US2930694A - Optical sensitization of direct positive emulsions - Google Patents

Optical sensitization of direct positive emulsions Download PDF

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Publication number
US2930694A
US2930694A US645544A US64554457A US2930694A US 2930694 A US2930694 A US 2930694A US 645544 A US645544 A US 645544A US 64554457 A US64554457 A US 64554457A US 2930694 A US2930694 A US 2930694A
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United States
Prior art keywords
grams
methyl
phenyl
hours
direct positive
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US645544A
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English (en)
Inventor
Coenen Max
Gotze Johannes
Grisar Ulrich
Riester Oskar
Stracke Werner
Zietan Karl
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Agfa Gevaert NV
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Agfa AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • G03C1/48584—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure spectrally sensitised

Definitions

  • this class includeswhole groups which have no sensitizing ability or which even have a desensitizing efiect.
  • the number of sensitizers which can be used in practice is further restricted by the fact that there is a large num ber of other requirements concerning the way in which the sensitizer operates when incorporated into silver halide emulsion layers.
  • the clearness of the layers and of the images produced therein must not be reduced and stability on storage, particularly as regards freedom from fogging and intensity of sensitization, must be guaranteed.
  • the gradation in both the fresh and in the aged condition must have the required value and must not change. 1
  • the color couplers may be present in the emulsion and these in many cases impair the sensitizing action, whereby the number of dyes which can be used is still further reduced.
  • the silverhalide emulsions used are those which show the solarization effect, that is to say produce a direct positive silver, image when exposed to the object to be reproduced and then developed in a silver halide developing solution. It has actually been found that with direct positive; emulsions containing color formers the sensitizers which have formerly been proposed for color photography can be used with only slight success or cannotbe used at all.
  • X is an anion, such as 01-, Br, I-, 010,-, cn so em -so,-
  • C H-C H CH CaHs H509 l CH3 It is further found that the introduction of the phenyl nuclei has an extremely favorable influence on the sensitizing eifect with respect to direct positive emulsions.
  • Fig. 1 shows the sensitization of dye II, and Fig. 2 that of dye III.
  • Fig. 4 shows the sensitization curve of dye V
  • Fig. 5 shows the sensitivity of dye VII.
  • Dye VIII absorbs at-645 m the sensitization maximum is at 670-680 111,14, and dye IX absorbs at 650 mu.
  • the dyestufis illustrated in the above formulae were dissolved in methanol and added to a direct positive emulsion in quantities of-60 mg. per -1 kg. of emulsion.
  • the dyes are dyes which arelnot substituted in the methine chain, they are produced either by known processes, for example according to W. Konig, J.pr.Ch. (2), 84, page 216; (2),, 87, page 241; Brooker, J. Amer. Chem. Soc. 62 (1940), page 1116, by reacting the corresponding indoles with fi-ethoxyacrolein acetal, or, if they are unsymmetrical dyes of the type V, VI, VIII, or IX, by reacting ketones,for example of the formulae- CHa such as -can.-be obtained for example according to German patent specification No.
  • Hg prepared from the n-methyl-phenyl-hydrazone of p-methoxy acetophenone by melting with zinc chloride at 180 C
  • 60 grams of benzanilide and 135 grams of phosphoric oxychloride are heated to 105 C. for 5 hours.
  • the melt is then decomposed by boiling with 3 litres of hydrochloric acid for 2 hours and immediately poured onto ice.
  • the precipitated mass is filtered ed with suction, covered with ethanol and filtered off once more with suction after 12 hours.
  • the residue can be recrystallized from about 1 litre of ethanol.
  • 62 grams of ketone of the melting point 134 C. are obtained.
  • the absorptionmaxirnum of the dyestuif in methanolic solution is 625 (4) DYESTUFF OF THE FORMULA VI (1 methyl 2 phenylindolyl 3)[1 methyl-2'-(pmethoxy-phenyl) indolyl 3l-a-(p-methoxy phenyl)-trimethine cyanin'e perchlorate (a) l-methyl 2 Q phenyl-3-p-methoxy-benzoyl-indole:
  • the absorption maximum in methanolic solution is 625 mu.
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one in. which:
  • R is an alkyl radical
  • R is a member'of the group consisting of a hydrogen atom, an alkyl radical, an alkoxy radical, and a halogen atom,
  • R" is a member of the group consisting of a hydrogen atom, an alkyl, cycloalkyl, thienyl, and RC H radical,
  • R is a member of the class consisting of a hydrogen atom and a methoxy radical
  • X stands for an anion
  • a photographic material comprising a direct positive silver halide emulsion layer containing a color coupler capable of reacting with the oxidation product of a primary aromatic amino developing agent to form a dye,- and also containing at least one optical sensitizer of the general formula:
  • R is' a member of the group consisting of a hydrogen atom, an alkyl radical, an alkoxy radical, and a halogen atom,
  • R is a member of the group consisting of a hydrogen atom; an alkyl, cycloalkyl, thienyl, and R-C ;H -v radical,
  • R is a'member of the class consisting of a hydrogen atom. and amethoxy radical
  • a photographic. material comprising a direct posi- The absorp tive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a dired; positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:
  • a photographic material comprising a direct positive silver halide emulsion layer containing at least one optical sensitizer of the general formula:

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US645544A 1956-03-19 1957-03-12 Optical sensitization of direct positive emulsions Expired - Lifetime US2930694A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA24514A DE1008118B (de) 1956-03-19 1956-03-19 Verfahren zur Sensibilisierung von Farbbildner enthaltenden Direktpositiv-Emulsionen

Publications (1)

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US2930694A true US2930694A (en) 1960-03-29

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US (1) US2930694A (en))
BE (1) BE555921A (en))
CH (1) CH355026A (en))
DE (1) DE1008118B (en))
FR (1) FR1177726A (en))
GB (1) GB825965A (en))

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3084045A (en) * 1957-03-28 1963-04-02 Agfa Ag Cyanine dyes derived from thienylben-zothiazoles and silver halide emulsions sensitized therewith
US3227552A (en) * 1960-05-13 1966-01-04 Eastman Kodak Co Preparation of photographic direct positive color images
US3501312A (en) * 1968-07-22 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing trimethine cyanine dyes
US3501310A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing compounds which accept electrons and spectrally sensitize the emulsion
US3501309A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing halogenated cyanine dyes
DE1803713B1 (de) * 1967-10-19 1970-10-01 Eastman Kodak Co Verfahren zur Herstellung von Trimethinindolfarbstoffen
US3541089A (en) * 1967-10-19 1970-11-17 Eastman Kodak Co Method of preparing chain-substituted trimethine indole dyestuffs
DE2429230A1 (de) * 1973-06-18 1975-01-09 Minnesota Mining & Mfg Cyanine und ihre verwendung in photographischem aufzeichnungsmaterial
US3963494A (en) * 1973-01-25 1976-06-15 Agfa-Gevaert N.V. Photographic multilayer direct-positive silver halide element

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2126078A (en) * 1932-04-26 1938-08-09 Agfa Ansco Corp Sensitizing photographic emulsion
US2640776A (en) * 1947-08-29 1953-06-02 Eastman Kodak Co Sensitized photographic emulsion containing color couplers
US2688545A (en) * 1953-05-28 1954-09-07 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2126078A (en) * 1932-04-26 1938-08-09 Agfa Ansco Corp Sensitizing photographic emulsion
US2640776A (en) * 1947-08-29 1953-06-02 Eastman Kodak Co Sensitized photographic emulsion containing color couplers
US2688545A (en) * 1953-05-28 1954-09-07 Eastman Kodak Co Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3084045A (en) * 1957-03-28 1963-04-02 Agfa Ag Cyanine dyes derived from thienylben-zothiazoles and silver halide emulsions sensitized therewith
US3227552A (en) * 1960-05-13 1966-01-04 Eastman Kodak Co Preparation of photographic direct positive color images
US3501310A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing compounds which accept electrons and spectrally sensitize the emulsion
US3501309A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing halogenated cyanine dyes
DE1803713B1 (de) * 1967-10-19 1970-10-01 Eastman Kodak Co Verfahren zur Herstellung von Trimethinindolfarbstoffen
US3541089A (en) * 1967-10-19 1970-11-17 Eastman Kodak Co Method of preparing chain-substituted trimethine indole dyestuffs
US3501312A (en) * 1968-07-22 1970-03-17 Eastman Kodak Co Direct positive silver halide emulsions containing trimethine cyanine dyes
US3963494A (en) * 1973-01-25 1976-06-15 Agfa-Gevaert N.V. Photographic multilayer direct-positive silver halide element
DE2429230A1 (de) * 1973-06-18 1975-01-09 Minnesota Mining & Mfg Cyanine und ihre verwendung in photographischem aufzeichnungsmaterial

Also Published As

Publication number Publication date
DE1008118B (de) 1957-05-09
CH355026A (de) 1961-06-15
BE555921A (en))
GB825965A (en) 1959-12-23
FR1177726A (fr) 1959-04-29

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